Graft polymer-fortified bitumen additives



United States Patent Ofitice GRAFT POLYMER-FORTIFIED' BrrUMEN ADDITIVESMathew L. Kalinowski, Chicago, and Lowell T. Crews, Homewood, Ill.,assignors to Standard Oil Company, Chicago, Ill., a corporation ofIndiana N Drawing. Application July 30, 1954, Serial No. 446,965

' Claims. (Cl. 260-4045) The present invention is directed toimprovements it bitumen compositions, and particularly to improvementsin mineral aggregate coating compositions, and more particularly relatesto bitumen compositions having improved adherence to damp or wet mineralaggregates, and to improvements in the method of making suchcompositions.

Residual oils and/or bituminous materials used in the preparation ofpavements and roads do not coat and adhere well to mineral aggregatesunless the-aggregate is substantially dry, and for this reason, inconventional pavements or road construction practice, it is customary todry the mineral aggregate by suitable well known methods; Furthermore,water entering the road or pavement during service may have adetrimental etfect in that it may displace the oil or bitumen from thesurface of the aggregate and thus diminish the bonding effect of the oiland/or bitumen. This materially shortens the life of the road orpavement requiring frequent repairs and is, therefore, uneconomical.

Mineral aggregates employed in road or pavement construction range incharacter from hydrophilic to hydrophobic. In general, siliceous andacidic minerals, such as sands and gravels, tend to be hydrophobic,while calcareous alkaline minerals, such as limestone, tend to behydrophilic. It has been observed that the mineral aggregates appear tohave a greater attraction for water than for oil or bitumens and that itis difiicult to obtain, by conventional methods, complete orsatisfactory coating of aggregates by oil or bitumen when water ispresent. Furthermore, even though satisfactory coating is obtained byusing dry aggregate, the oil or bitumen tends to be displaced if waterenters the pavement or road.

It is known that the coating of damp or Wet mineral aggregates by oil orbitumen may be efiected and the resistance of the coating todisplacement or stripping by water improved by treating the aggregatewith small amounts of a water-soluble soap of a fatty acid inconjunction with a water-soluble salt of a polyvalent heavy metal oractivator. For optimum results with these reagents, the relative amountsof the two reagents must be carefully adjusted. Thus, when a divalentheavy metal is used as activator, the amount of soap used should besubstantially one mole per mole of activator; with a trivalent metal,between one and two moles of soap per mole of activator. Use of largeramounts of soap than this diminishes the eifect obtained, and thisdiminution of effect increases with excess of soap over the proportionsgiven until, When the amount of soap becomes equivalent to theactivator, i. e., two moles of soap per mole of divalent metal or threeper mole of trivalent metal, the beneficial effect of the reagentsubstantially disappears.

The above method hasthe disadvantage that the relaare critical and mustbe carefully adjusted for optimum results. Use of an excess of soap overthe optimum amount diminishes rather than enhances the eifect obtained;the use ofexcess heavy metal to avoid the danger of excess soap is notharmful but increases the cost. Furthermore, the two reagents must beweighed or measured out and added to each batch, as neither is solublein the oil or bitumen; while this disadvantage may be partially overcomeunder favorable conditions by using, in place of the soap, a fatty aciddissolved in the oil or bitumen, this expedient is effective only underfavorable conditions of low moisture content of the aggregate, adequateand eflicient mixing, etc. Under conditions which are not at all severe,such as appreciable amounts of water and/ or facilities for onlymoderately eflicient mixing, fatty acids appear not to be suflicientlysoluble in water to reach and react with the heavy metal ion to therequiredextent, and if added directly to the mixture or dissolved in theoil or bitumen, are practically without effect.

Another important disadvantage of the above method is that a heavypolyvalent metal salt must be-used with the. soap. Furthermore, it hasbeen found that while some limestones appear capable of adsorbing orreacting with polyvalent heavy metal ions and accordingly respond tosome degree to the above method, a great many others do not, and withthese it is diiiicult or impossible to obtain a good coating by theabove method. Also, since the foregoing method is not in generalsatisfactory with limestone, a great many natural mixed aggregates suchas gravels containing both siliceous and calcareous particles will haveonly a portion of the particles coated.

In addition to the use of polyvalent fatty acid soaps in bitumens asmineral aggregate coating agents, certain organic nitrogen compounds,such as those obtained by reacting a polyamine with a fatty acid underconditions to form essentially amides, have been used for this purpose.However, although the amide-type asphalt additives are effective coatingagents for acidic mineral aggregates, such as sands and gravels, theyare inefiective on alkaline mineral aggregates such as limestone. It isa primary object of this invention to avoid the formation of amides inthe preparation of the fatty acid-amine type additive for bitumens andthereby retain the effectiveness of the additive in fortifying thecoating material for application to acidic and alkaline aggregate.Another object of the present invention is to provide a coatingcomposition for acidic and alkaline mineral aggregates which will not bestripped therefrom by aqueous liquids. Still another object of theinvention is to provide a coating composition for acidic and alkalinemineral aggregate-s which can be applied without the necessity of dryingthe mineral aggregate and which will adhere thereto even in a wetcondition. Another object of the invention is to provide a method ofpreventing stripping of the coating composition from acidic and alkalinemineral aggregates by water after the road and/or pavement isconstructed. A further object of the invention is to provide a method ofpromoting the adherence of oil bituminous materials to siliceous andlimestone aggregates without the necessity of drying the same. Otherobjects and advantages of the invention will become apparent asdescription thereof proceeds.

In accordance with the present invention, bitumens, such as for example,road oils and asphalts having improved mineral aggregate coatingproperties, especially with respect to wet acidic and alkaline mineralaggregates, are obtained by incorporating in such bitumens from aboutPatented Nov. 5,

3 0.25% to about and preferably from about 0.5% to about 3%, by weight,based on the bitumen, of the product obtained by reacting, in thepresence of an ethylene oxide-propylene oxide graft polymer, analiphatic polyamine having from 2 to about 20 carbon atoms per moleculewith the propane-insoluble fraction obtained inthe propane extraction ofcrude fatty materials, such as animal, marine and vegetable fats, fattyoils or fatty acids split therefrom, under conditions which avoid theformation of amides so that a product essentially free of amido groupsis obtained. Since amidation of amine soaps is brought about by the lossof water at high temperatures, the reaction of the aliphatic polyaminewith the aforementioned propane-insoluble fraction is carried out attempera tures below about 150 F., preferably below about 125 F and morepreferably at substantially ambient temperatures of from about 60 F. toabout 125 F., for example about 100 F. to about 125 F., and for acontact time of from about hour to 1.0 hour.

We have discovered that the addition to the mixture of alkylenepolyamine and propane-insoluble fractions of a relatively small amountof an ethylene oxide-propylene oxide graft polymer corresponding to thegeneral formula HO(C2H40)a(C3H60)b(C2H40)c-H of molecular weight withinthe range of about 1000 to about 4500 wherein a, b, and c are integers,the sum of a and 0 being within the range of about 2 to about 20, and bhaving a value of from about to 60, makes possible the production ofvery effective asphalt additive at relatively low temperatures..Thisnonionic graft polymer is prepared as follows: polyoxypropyleneglycol is made by condensing propylene oxide in the presence of moistureor by con densing propylene glycol in the presence of a catalytic amountof sodium hydroxide. The polyoxypropylene glycol is then reacted withethylene oxide to produce the ethylene oxide-propylene oxide graftpolymer. These products are known commercially as Pluronics and areproduced by the Wyandotte Chemical Company.

Stripping properties of bitumen coating material containing reactionproduct prepared from the propane-insoluble material-aliphatic aminereaction product in the presence of the nonionic polymer are excellent.The reaction mixture containing the nonionic polymer is less viscousthan reaction mixtures containing the propaneinsoluble fraction andaliphatic polyamine reaction prodnot without the added nonionic polymerand hence the processing and transfer of the additive product by pumpingand incorporation of the product in the asphalt coating material isgreatly facilitated when the nonionic polymer is present in theadditive. The nonionic polymer is incorporated in the reaction mixturein amounts to correspond to about 0.5% to about 10% by weight of thepropane-insoluble (Ebony Fat as defined below)- alkylene polyaminereaction product. The addition of the nonionic polymer may be made tothe heated dispersion of Ebony Fat in hydrocarbon oil diluent or to anaromatic hydrocarbon-rich hydrocarbon oil dispersion of the aliphaticpolyamine. The presence of the polymer at the time of initial contact ofthe propane-insoluble component with the polyamine makes possible thesubstantial completion of the reaction at substantiallyambienttemperatures in a relatively short time, usually less than 30minutes when temperatures. of about 125 F. are employed, thus avoidingamide formation.

The propane-insoluble fraction'obtained in the propane extraction ofcrude fatty materials of the type above described contains, inadditionto fats and fatty acids, esters of fatty acids and sterols. Thesepropane-insoluble fractions which are obtained as residue of the orderof about 0.2% to about 10%, by weight, contain most of the color bodieswhich are present in the crude fatty materials, and because of theirvery dark color, are referred to in' commerce as Ebony Fats. Theproperties of representative samples of thepropane-insoluble residuesobtained from animal fats and from vegetable oils, on a water-freebasis, are approximately as follows:

Residue Residue Property from from Animal Vegetable Fat 011 Viscosity,Seconds Saybolt at 100 F. 6, 500 930 Viscosity, Seconds Saybolt at 130F. 1, 860 430 Viscosity, Seconds Saybolt at 210 F. 300 100 Ash. Weightpercent 1. 3 06 A.P.I. Gravity, degrees 10 1G Acidity, A.S.T.M. (D4364)Mg. KOH/gm.. 41 G3 Pentane Insoluble, Weight pereent 2. 6 4.2 BenzeneInsoluble, Weight percent .7 1.0 Sapomfication Number 190 170 Fatty Acid31 Iodine Number 58 106 The above properties are, of course, merelyillustrative,

and it should be understood that both the amount and the 5i vegetablefatty materials with propane to obtain Ebony Fat" is well known to thoseskilled in the art and one example thereof is commonly referred to asthe Solexol Process, currently and commercially used and described inIndustrial and Engineering Chemistry" of February 1949, page 280. Thesystem for effecting such extractive fractionation is described indetail in U. S. 2,505,338 and U. S. 2,521,234. For most crude animalfats, marine oils and vegetable oils, and similar fatty materialsincluding acids split from such fats, the fractionation conditions areemployed which givea propane-insoluble residue of about 1%, i. e., about0.2% to about 2%, although in some cases such residues may be as largeas 5% or even 10%. i The amine reactant employed in preparing theadditive of the present invention is an aliphatic polyamine,particularly an alkylene polyamine containing at least two primary aminonitrogen atoms. Examples of alkylene polyamines suitable for theherein-described purpose are ethylene diamine, propylene diamine,diethylene triamine diamylene triamine, triethylene tetramine,tripropylene tetramine, diethylenepropylene tetramine, tetraethylenepentamine, tetrabutylene pentamine, diethylenedipropylene pentamine,butylene diamine, dihcxylene triamine, and the like, or mixturesthereof. For example, a suitable polyamine product is a crude diethylenetriamine containing minor amounts of ethylene diamine and triethylenetetramine. Other suitable polyamines include those having the generalformula RNH( CH2 sNHz in which R is preferablya Cw to C18 aliphaticchain, and which are obtained by condensing the suitable amine withacrylonitrile andhydrogenating to the corresponding diamine.Commercially available polyamines of this type are those marketed byArmour and Company as Duomeens, which are prepared by the condensationof a dodecyl (coco) amine or an octadecyl (tallow) amine withacrylonitrile, followed by hydrogenation to the corresponding diamineproduct; these products are marketed as Duomeen C and Duomeen T,respectively.

In the preparation of the Ebony Fat and polyamine reaction product, itis, preferable, although not essential, that the Ebony Fat be firstdehydrated to obtain an essentially water-free product, or a producthaving not more than about 0.5% water. This can be readily accomplishedby diluting the Ebony Fat with from about 10% to about 200% of asuitable hydrocarbon solvent,

by heating the diluted mixture at a temperatureof about" 210 F. to 290F. while stirring and/or blowing with air or other suitable gaseousmedium until the water content has been reduced to the desired value.Following the dehydrogenation step the Ebony Fat-graft polymeroilmixture is cooled to a temperature below about 150 F., preferably by thecontinued inert gas blow such as for example a passage therethrough ofcold air. If the Ebony Fat contains an undesirable amount ofcontaminants, they can be removed by permitting the hot dehydratedsolution to settle, and decanting the di-' luted solution of purifiedEbony Fat. If desired, the diluent may be removed from the dehydratedEbony Fat by suitable means, such as by distillation under vacuum;however, we prefer to react the diluted Ebony Fats with the polyamine.As indicated above, this dehydration of the Ebony Fat may be carried outin the presence of the added nonionic polymer or if the Ebony Fatcontains undesirable contaminants the polymer may be added .to thedecanted solution? of dehydrated Ebony Fat. 7

Aromatic-rich hydrocarbon solvents suitable for this purpose arepreferably those having boiling points, above about 220 F. atatmospheric pressure, for example, from about 220 F. to about 600 F.,and includesmononuclear aromatic hydrocarbons or condensed ring armmatics, such as naphthalenes and mixtures of the higher boilingmononuclear aromatic hydrocarbons and polynuclear aromatic hydrocarbons.A preferred source of mixed aromatic hydrocarbons, suitable for thepurpose, is a light catalytic cycle stock obtained from a powdered ora'fluid-type catalytic-type hydrocarbon cracking operation in which gasoil or heavier hydrocarbons are cracked at a temperature of 800 F. to1050 F. under a pressure of about atmospheric to 50 pounds per squareinch, in the presence ofsuitable fluidized powdered catalyst, such asfor example silicaalumina, silica magnesia, and other well-knowncracking catalysts. A method of conducting a fluidized crackingoperation is described in U. S. 2,341,193, issued to Fred W. Scheineman,February 8, 1944. Fractions from the process heavier than gasoline,depending upon their boiling range, are commonly referred to as lightcatalytic cycle stock, heavy catalytic cycle stock and catalytic recycleresid, which usually are cycled to cracking. A li ht catalytic cyclestock particularly well suited as a diluent for the dehydration of theEbony Pat is a fraction having an aromatic content of at least about 40%and a distillation range between about 425 F. and 560 F. A typicalanalysis of a suitable light catalytic cycle stock shows the material tobe composed substantially of about 10% normal C12 to C20 parafiins,about 45% of other parafiins, and naphthenes, about mono-nucleararomatics, which are mainly monoto hexa-alkylated benzenes, and about40% polynuclear aromatics, which are mainly alkyl naphthalenes, largelymethylated naphthalenes. While we prefer to use a light catalytic cyclestock of the type described, hydrocarbon fractions from other catalyticconversion processes or thermal hydrocarbon conversion processes aresuitable, provided they have an aromatic content of at least about 20%,and a distillation range of above about 220 F. If desired, a part of thebitumen coating material, if a road oil, may be used as diluent for theEbony Fat for the dehydrating operation either in the presence orabsence of the nonionic polymer.

The dehydrated Ebony Fat preferably containing the nonionic polymer andpreferably, but not necessarily, in solution in the light catalyticcycle stock or other suitable diluent, is reacted with the polyamineinthe ratio of from about 20:1 to about 5:1, and preferably in a ratio offrom about 12:1 Ebony Fat to the polyamine, at a temperature of about 60F..to about 150 F., for example from about 100 F. to about 125 F., fornot more than about one hour. If desired, the polyaminemay be added tothe Ebony Fatin the form of a dispersion in a hydrocarbon oil,preferably an aromatic hydrocarbonrich hydrocarbon oil containingdispersed therein the nonionic ethylene oxide-propylene oxide polymer.By conducting the reaction in the manner herein described, andmaintaining the finished product, until ready for use, at a temperaturebelow about 150 F. and preferably below about 125 R, an eflicient stablecoating agent essentially free of amido groups is obtained.

The preparation of polyamine-Ebony Fat reaction products is illustratedby the following examples:

EXAMPLE I A hydrocarbon oil solution of Ebony Fat consisting of 61partsby weight of Ebony Fat and 39 parts by weight of light catalyticcycle stock was dehydrated according to the above procedure. Theequivalent weight of the dehydrated solution was 1212. To 303 grams ofthe dehydrated solution, that is, equivalent weight, was added a mixtureof 17.5 grams of crude diethylenetriamine (equivalent weight 56) dilutedwith 71 grams of light catalytic cycle stock. The reaction mixture wasintimately contacted by mechanical stirring at 120 F. for a period of 15minutes. The reaction mixture was used as a control sample in comparingthe performance of the reaction product prepared in Example II.

As indicated in Example I, a 25% excess of the polyamine over thatrequired to react with the Ebony Fat was used. In general, we use fromabout 5% to about 50%, preferably about 25%, excess amine in preparingthe Ebony Fat-alkylene polyamine reaction product containing theassociated nonionic graft polymer.

EXAMPLE II To 303 grams of the Ebony Fat stock solution prepared as inExample I was added a dispersion of 17.5 grams of crude diethylenetriamine in 66 grams of light catalytic cycle stock containing dispersedtherein 5 grams of Pluronic-62 having a molecular weight of about 2900,and showing by analysis an oxygen content of about 29.8%, that is, theapparent value of (a+c) of this product in the above general formula isabout 13 and of b is about 40. The mixture was intimately contacted fora period of 15 minutes at a temperature of 120 F.

Samples of the products produced in Examples 1 and II were used in thetests described below.

While we have not been able to definitely determine the composition ofthe Ebony Fat-polyamine reaction product, we believe the reactionproduct comprises essentially the amine soaps of the fatty acidscontained in the Ebony Fat, together with unreacted esters and alcohols,i. e., sterols. The presence of from about 0.25% to 10% 1 by weight ofthe nonionic polymer (based on the weight of the reaction product)improves the stripping properties of the coating material to which thereaction product is added. The reaction mixture, exclusive of diluentoil, will usually consist essentially of from about 65% to about byweight of Ebony Fat, as defined hereinabove, from about 5% to about 25%by weight of polyamine reactant, and from about 0.2% to about 10% byweight of the nonionic polymer.

The asphalt component of the herein described composition may be anybitumen which is useful for the coating of mineral aggregates used inthe making of roads, highways, etc., or for the coating of othermaterials or surfaces where a water-resistant bond between the surfaceand the asphalt is advantageous or necessary. The term asphalt asemployed herein is intended to be synonymous with bitumen and to cover aliquid, semi-solid, or solid plastic bituminous material of the typeemployed in making or surfacing of highways and/or pavements, caulkingagents, sealing compounds, water impervious paints, roofing materials,etc. Such asphalt or bituminous materials are mixtures of hydrocarbonsof natural or pyrogenous origin, and are usually derived from petroleumor coal but may occur as such in nature. Asphalts V may be derived asdistillation resids or cracking resids with or without oxidation byair-blowing or by catalytic A specific example of a liquid asphalt ofoxidation.

the type commonly employed in the preparation of highways,.etc., is apetroleum residuum fiuxed with a light aromatic diluent boiling in therange of 400 'F. to 700 F. to give a cut-back product of the followingspecifi Tests on distillation:

Residue- ASTM penetration at 77 F 120-300. ASTM ductility at 77 F NLT100. S01. in CCl4, percent NLT 99.5. Oliensis spot test Negative.

' Not less than.

I Not more than.

Normally solid paving asp halts of the 40 to 200 penetrations gradescommonly used in road building fallwith in the following specifications:

40-200. Not less than 100. 7 Negative.

Not less than 99.5. Not less than 0.9901.000. Not less than 475.

Not more than 0.5.

Not less than 70-75.

The effectiveness of the herein described Ebony Fatpolyamine reactionproducts in enhancing the adhesion of asphalts to wet mineralaggregrates is determined by subjecting blends of asphalts and thedescribed reaction products to one or more of the following tests:

A. Modified Colorado Coating Tests Twenty grams of Ottawa sand or 20grams of a 20 to 35 mesh limestone are weighed into a 2 oz. containerand covered with one-half inch of distilled water.

One

gram of the additive-containing asphalt is floated on the water, themixture then shaken for thirty seconds, and the extent of coatingdetermined by visual'inspection; the results are expressed as PercentCoated.

B. Wyoming Stripping Test Approximately 25 grams of Lander chips,allpassing the in. sieve and retained on the No. 4 sieve, is mixed byhand with 1.0 gram of fortified asphalt until the best possible coatingis obtained.

The mix is placed in an oven at 140 F. for 18 to 24 hours after which itis thoroughly remixed and is allowed to cool to room temperature. The

sample is then immersed in distilled water at a temperature of 120 F.,and is maintained at this temperature. for a period of 24 hours. At theend of this period the area of the aggregate remaining coated isdetermined visually while the sample is still under water. Any thin ortranslucent areas are considered to be coated. The Wyoming HighwayDepartment requires that 80% or greater coat-.

ing be retained in this test.

Samples of the above-described liquid asphalt designated as MC (mediumcuring)-2 asphalt containing sufiicient diluted additive, as describedin Examples I and II above, to provide 1.0% and 2.0% by weight of theactive additive based on the medium curing asphalt (MC-2),

were tested in the Modified Colorado Coating Test and Wyoming StrippingTest. The results are given in Table I below:

TABLE I Coating Additive Strip- Additlve in MIC-2 Cone, ping, percentSan Limepercent percent stone. 10 percent None 0 0 10 I 1 25 90 40 2 6090 80 H 1 50 90 50 2 85 90 95 PluronicL-GZ 1 2 5 5 10 The results inTable I show the superiority of the asphalt containing the nonionicpolymer associated with the Ebony Fat+alkyleneaminereaction productadditive particularly at the 2% level additive concentration.

The concentration of nonionic polymer in the additive was about 2.5%based on the weight of the reaction product in the asphalt and about0.025% and 0.05% by weight respectively in the asphalt at the 1.0% and2.0% levels of concentration of active additive in the asphalt.

Heat stability of the additives prepared in Examples I and H were testedby heating and stirring these samples of additive for varying lengths oftime at 210 F. and retesting asphalts containing the reheated additivefor coating ability and stripping resistance. The results are shown inTable II. v

TABLE II Time Sand Limestone Stripping Additive in MC-2 Slllll;8%&t

minutes 1% 2% 1% 2% 1% 2% Per- Per- Per- Per- Per- Percent cent centcent cent cent 0 25 so 90 90 so 90 a0 90 no 95 3o 85 120 30 95 so 95 so05 150 25 9s 85 no as 0 50 90 so as 30 75 05 so 00 05 90 75 95 so 95 so05 75 95 s5 9s 70 95 75 100 so 95 0s 95 1 Percentages indicate percentsurface remaining covered by coating material.

The coating ability and stripping qualities of the asphalt containingthe reaction product and associated nonionic polymerwas not adverselyaffected by the heat treatment at the 2% concentration level and coatingability for sand at the 1% concentration level was much better than thecoating shown in Example I. On the other hand, the heat treatment of thereaction product containing no associated nonionic polymer resulted inlowering the coating ability of the asphalt to which the additive wasadded below that of non-heated additive and the stripping properties ofthe asphalt were inferior to the stripreaction product containing thenonionic polymer.

Having thsu described our invention, we claim: 1. In the process forpreparing. an additive suitable for use in bitumen comprising reactingat least one alkylene ping properties of the asphalt to whichthe heattreated polyarnine, having from 2 to about 20 carbon atoms, with EbonyFat, which Ebony Fat is the propane-insoluble residue obtained in thesolvent extraction of a crude fatty material selected from the classconsisting of crude animal fats, fatty oils and fatty acids, crudevegetable fats,

fatty oils, and fatty acids, and mixtures thereof with action productbeing essentially free of amido groups, the improvement which comprisesincorporating in the reaction mixture of said Ebony Fat and alkylenepolyamine from about 0.5% to about by weight based on the weight of saidEbony Fat and alkylene polyamine in said reaction mixture, of anethylene oxide-propylene oxide graft polymer corresponding to thegeneral formula HO(C2H40)a(c3H60)b(C2H40)cH and having a molecularweight of about 1000 to about 4500 wherein a, b, and c are integers, thesum of a and c being within the range of about 2 to about 20 and bhaving a value within the range of about to about 60, and maintainingsaid reaction mixture at a temperature of from about 60 F. to about 150F.

2. The improvement as described in claim 1 wherein the Ebony Fat isdehydrated to a water content not more than about 0.5% before contactwith the alkylene polyamine to form said mixture of Ebony Fat with saidalkylene polyamine.

3. The improvement as described in claim 1 wherein the reaction of theEbony Fat with the alkylene polyamine containing said incorporated graftpolymer is carried out in the presence of an aromatic hydrocarbon-richhydrocarbon diluent.

4. The improvement as described in claim 1 wherein the alkylene aminecomponent of the reaction mixture is crude diethylene triaminecontaining minor amounts of ethylene diamine and triethylene tetramine.

5. The improvement as described in claim 1 wherein the ratio by weightof Ebony Fat to alkylene polyamine in the reaction mixture is within therange of :1 to about 5: 1.

6. In the process for preparing an additive suitable for use in bitumencomprising reacting at least one alkylene polyamine, having from 2 toabout 20 carbon atoms, with Ebony Fat, which Ebony Fat is the propaneinsoluble residue obtained in the solvent extraction of a crude fattymaterial selected from the class consisting of crude animal fats, fattyoils, and fatty acids, crude vegetable fats, fatty oils, and fattyacids, and mixtures thereof with liquified propane, said insolubleresidue being insoluble in 6 to volumes of propane at a temperature offrom about 140 F. to about 190 F. and constituting from about 0.2% toabout 10% of the crude fatty material from which said insoluble residueis extracted, said reaction product being essentially free of amidogroups, the improvement which comprises the steps of (I) blowing with aninert gas at a temperature of about 210 F. to 290 F. an intimate mixtureof a hydrocarbon oil diluent containing said Ebony Fat and an ethyleneoxide-propylene oxide graft polymer corresponding to the general formulaHO(C2H40)a(c3H60)b(C2H40)cH and having a molecular weight of about 2900wherein a, b, and c are integers, the sum of a and 0 being about 13 andb being about 40 to reduce the moisture content of said Ebony Fat to avalue not greater than about 0.5%, (2) cooling the product of step 1 toa temperature below about 150 F., (3) adding to the dried, cooledproduct of step 2 sufficient alkylene polyamine to provide a reactionmixture containing an excess of the alkylene polyamine over thatrequired to react with said Ebony Fat" and (4) intimately contacting theEbony Fat" and alkylene polyamine of the reaction mixture at atemperature below about 150 F.

7. The improvement as described in claim 6 wherein the amount of graftpolymer in the hydrocarbon diluent is within the range of from about 0.5to about 10% by 10 weight of the Ebony Fat plus alkylene polyaminereactants in said diluent.

8. The process of claim 6 wherein the diluent is a hydrocarbon oil richin aromatic hydrocarbons.

9. The method of preparing a hydrocarbon oil-diluted reaction productsuitable for use as a bitumen additive comprising the reaction productof at least one alkylene polyamine, having from 2 to about 20 carbonatoms, with Ebony Fat, which Ebony Fat is the propaneinsoluble residueobtained in the solvent extraction of a crude fatty material selectedfrom the class consisting of crude animal fats, fatty oils, and fattyacids, crude vegetable fats, fatty oils, and fatty acids and mixturesthereof, with liquified propane, said insoluble residue being insolublein 6 to 30 volumes of propane at a temperature of from about F. to about190 F. and constituting from about 0.2% to about 10% of the crude fattymaterial from which said insoluble residue is extracted, said reactionproduct being essentially free of amido groups, which method comprisesthe steps of (1) forming a mixture of said Ebony Fat in an aromatichydrocarbonrich hydrocarbon solvent boiling in the range of from about220 F. to about 600 F., (2) suspending said alkylene polyamine in anaromatic hydrocarbon-rich hydrocarbon solvent containing mixed thereinnonionic graft polymer corresponding to the general formulaHO(C2H40)a(C3H60)b(C2H40)cH and having a molecular Weight within therange of about 1000 to about 4500 wherein a, b, and c are integers, thesum of a and c being Within the range of about 2 to about 20 and bhaving a value within the range of from 15 to about 60, the amount ofsaid graft polymer mixed in said aromatic hydrocarbonrich hydrocarbonsolvent being sufiicient to provide in the reaction mixture of step 3below from about 0.5% to 10% by Weight of said reaction product of EbonyFat with alkylene polyamine, (3) intimately mixing at a temperaturewithin the range of about 60 F. to about F. the suspension of step 2with the mixture of step 1 to provide a stable graft polymer-dispersedreaction mixture containing Ebony Fat and alkylene polyamine inproportions to provide a ratio by weight of Ebony Fat to alkylenepolyamine within the range of from about 20:1 to about 5:1 in saidstably-dispersed reaction mixture, and (4) maintaining saidstably-dispersed reaction mixture ata temperature not in excess of about150 F. for a period of time sutficient to complete the reaction of EbonyFat with alkylene polyamine not in excess of one hour.

10. The bitumen additive consisting essentially of Ebony Fat-alkylenepolyamine reaction product, ethylene oxide-propylene oxide graft polymerand hydrocarbon diluent produced as described in claim 6.

References Cited in the file of this patent UNITED STATES PATENTS2,438,318 Johnson Mar. 23, 1948 2,521,234 Leaders et al. Sept. 5, 19502,525,771 Cook et al. Oct. 17, 1950 2,663,648 Jelling Dec. 22, 19532,679,462 Monson May 25, 1954 2,728,682 Kalinowski et al Dec. 27, 19552,736,658 Pfohl Feb. 28, 1956 OTHER REFERENCES Schwartz et al.: SurfaceActive Agents, 1949, pages 202-207, 501.

1. IN THE PROCESS OF PREPARING AN ADDITIVE SUITABLE FOR USE IN BITUMEN COMPISISING REACTING AT LEAST ONE ALKYLENE POLYAMINE, HAVING FROM 2 TO ABOUT 20 CARBON ATOMS, WITH "EBONY FAT", WHICH "EBONY FAT" IS THE PROPANE-INSOLUBLE RESIDUE OBTAINED IN THE SOLVENT EXTRACTION OF A CRUDE FATTY MATERIAL SELECTED FROM THE CLASS CONSISTING OF CRUDE ANIMAL FATS, FATTY OILS AND FATTY ACIDS, CRUDE VEGATABLE FATS, FATTY OILS, AND FATTY ACIDS, AND MIXTURES THEREOF WITH LIQUIFIED PROPANE, SAID INSOLUBLE RESIDUE BEING INSOLUBLE IN 6 TO 30 VOLUMES OF PROPANE AT A TEMPERATURE OF FROM ABOUT 140*F. TO ABOUT 190*F. AND CONSTITUTING FROM ABOUT 0.2% TO ABOUT 10% OF THE CRUDE FATTY MATERIAL FROM WHICH SAID INSOLUBLE RESIDUE IS EXTRACTED, SAID REACTION PRODUCT BEING ESSENTIALLY FREE OF AMINO GROUPS, THE IMPROVEMENT WHICH COMPRISES INCORPORATING IN THE REACTION MIXTURE OF SAID "EBONY FAT" AND ALKYLENE POLYAMINE FROM ABOUT 0.5% TO ABOUT 10% BY WEIGHT BASED ON THE WEIGHT OF SAID "EBONY FAT" AND ALKLYLENE POLYAMINE IN SAID REACTION MIXTURE, OF AN ETHYLENE OXIDE-PROPYLENE OXIDE GRAFT POLYMER CORRESPONDING TO THE GENERAL FORMULA HO(C2H4O)A(C3H6O)B(C2H4O)C'' AND HAVING A MOLECULAR WEIGHT OF ABOUT 1000 TO ABOUT 4500 WHEREIN A,B, AND C ARE INTEGERS, THE SUM OF A AND C BEING WITHIN THE RANGE OF ABOUT 2 TO ABOUT 20 AND B HAVING A VALUE WITHIN THE RANGE OF ABOUT 15 TO ABOUT 60, AND MAINTAINING SAID REACTION MIXTURE AT A TEMPERATURE OF FROM ABOUT 60*F. TO ABOUT 150*F. 